This invention relates to polyamines and polymers made therewith suitable for use in manufacturing fibers, fabrics, films and other useful articles, and to the articles and methods of making such compositions and articles. This invention also relates to processes for preparing the polyamines and polymers and use thereof, including acid-dyeable polymer compositions made with the polymers.
Polyesters, especially polyalkylene terephthalates, have excellent physical and chemical properties and have been widely used for resins, films and fibers. In particular, polyester fibers have a high melting point, and can attain high orientation and crystallinity. Accordingly, polyesters have excellent fiber properties such as chemical, heat and light stability, and high strength. However, polyesters, especially polyester fibers and fabrics, are difficult to dye. The molecular structure and the high levels of orientation and crystallinity that impart the desirable properties to the polyester also contribute to a resistance to coloration by dye compounds. Also contributing to the difficulty in dyeing polyester compositions is the characteristic that polyesters do not have dye sites within the polymer chain that are reactive to basic or acid dye compounds.
Nylon polymers are generally dyed more easily than polyesters because of their greater permeability and, in the case of the preferred acid dyes, because the amine end groups in nylon serve as dyesites. However, in many cases these amine-end dyesites are not present at sufficiently high concentration to give the desired depth of dyeing, particularly in fine-denier fibers. Therefore, improvements in the acid dyeability of nylon are desired.
To impart acid dyeability to polyester, it has been proposed to blend polyester with nylon 6 or nylon 6,6 to obtain the benefits of the amine-end dyesites in the resulting polyester/polyamide copolymer composition. The high concentrations of polyamide that may be required to impart dyeability in this polyester/polyamide composition can result in forming polyamide microfibrils, which decrease the physical properties of the polyester/polyamide copolymer and create difficulties in processing.
Co-polymerizing nitrogen containing compounds into polyester chains to improve acid dyeability has been disclosed in, for instance, U.S. Pat. Nos. 3,901,853, 4,001,189 and 4,001,190.
Canadian Patent No. 974,340 discloses acid-dyeable polyester compositions comprising tertiary nitrogen-containing polyamides. Preferred are copolyamides of two or more monomers inclusive of diamines, dicarboxylic acids and aminocarboxylic acids. The tertiary nitrogen component may be derived from piperazine derivatives; HOOC(xe2x80x94CH2)nxe2x80x94NRxe2x80x94(CH2)nxe2x80x94COOH, wherein R can be a group selected from the class consisting of aliphatic (branched or unbranched), cycloaliphatic, aryl or heterocyclic groups; R1xe2x80x94NHxe2x80x94R2xe2x80x94NR3xe2x80x94R4xe2x80x94NHR5, wherein R2 and R4 can be a group selected from aliphatic (branched or unbranched), cycloaliphatic or aryl, R1 and R5 can be a group selected from hydrogen, aliphatic (branched or unbranched), cycloaliphatic or aryl, and R3 is aliphatic (branched or unbranched), cycloaliphatic, aryl or heterocyclic; and cyclic polyamines. Piperazine ring containing polyamides are preferred and all of the examples are directed to these compounds, and to their use with polyethylene terephthalate or polybutylene terephthalate. Piperazine ring containing polyamides, a cyclic compound containing two nitrogens on a single ring, is not sufficiently thermally stable for many applications.
WO 01/34693 (corresponding to co-pending U.S. patent application Ser. No. 09/708,209, filed Aug. 11, 2000 (Docket No. RD-7850)), discloses an acid-dyeable polyester composition made by melt-blending a polyester with a polymeric additive containing a secondary amine salt or a secondary amine, such as made by combining bis(hexamethylene)triamine with a second monomer unit such as a terephthalate. This technology is particularly useful for dyeing fabrics lightly, but adding 3-4 mole % or more of the dye has been found to impact physical properties, particularly tenacity. Tenacity is improved by adding phosphorous acid; however, phosphorous acid leads to instability of pack pressure and may cause spin problems over the long run. In addition, it was not possible to significantly increase the amount of BHMT added using phosphorus acid without spin problems. Therefore, an additive that can provide deep dyeable polyester with acid dyes without such drawbacks is desired.
U.S. Pat. No. 5,000,792 discloses a pigment dispersing agent comprising the polyester reaction product of a polyester having a free carboxyl group, of which the acid value is in the range of from 10 to 60, with an amine compound of the formula: NH2xe2x80x94R1xe2x80x94(NR3)xe2x80x94R2xe2x80x94NH2 wherein R1 and R2 are alkylene radicals which can be the same or different, each containing 2 to 6 carbon atoms, and R3 is a radical of the formula CH3xe2x80x94 or C2H5xe2x80x94. The dispersing agent is used to disperse pigments in paints and inks.
All of the aforementioned documents are incorporated herein by reference.
It is desirable to have acid-dyeable nitrogen-containing polymer compositions, particularly polyester and/or nylon compositions, with good physical properties which may be easily processed into fibers, films or other shaped articles and acid-dyed without expensive additives, special solutions, spinning problems, and/or complicated application procedures. It is particularly desirable to be able to deep dye such compositions or shaped articles.
This invention is directed to a polyamine having the formula:
H2Nxe2x80x94A[NRxe2x80x94B]aNH2
or salts thereof, wherein A and B, which may be the same or different, are selected from aliphatic or aromatic substituents provided that at least four carbon atoms separate any two nitrogen groups, R is an aliphatic or aromatic group, and a is 2 to 5.
In one preferred embodiment the polyamine is a salt and in another it is not a salt. Preferred salts are acid salts. The polyamine is preferably salinized with phosphorous acid, phosphoric acid, pyrophosphoric acid or phenyl phosphinic acid.
In a preferred embodiment, a is 2.
In a preferred embodiment, the polyamine is:
H2N(CH2)x[NR(CH2)y]aNH2
or salt thereof, wherein x and y, which may be the same or different, are 4 to 10, a is 2 to 5, and R is an alkyl group containing 1 to 8 carbons in a straight or branched chain. In one preferred embodiment, a is 2. In one preferred embodiment the polyamine is a salt and in another it is not a salt.
One preferred polyamine is dimethyltributylenetetramine. One preferred polyamine salt is the phosphorous salt of dimethyltributylenetetramine.
The invention is also directed to polymers having the formula: 
or salts thereof, wherein A, B and Q, which may be the same or different, are selected from aliphatic or aromatic substituents provided that at least four carbon atoms separate any two nitrogen groups, R is an aliphatic or aromatic group, a is greater than 1 to about 5, and n is 3 to about 1,000. Preferably, a is about 2 to about 5.
In one preferred embodiment the polymer is a salt and in another it is not a salt. Preferred salts are acid salts. The polymer is preferably salinized with phosphorous acid, phosphoric acid, pyrophosphoric acid or phenyl phosphinic acid.
Preferably, n is from 3 to about 100, more preferably n is from 3 to about 20.
Preferably, A, B and Q are selected from alkylene substituents containing from 4 to 20 carbons and arylene substituents containing from 6 to 18 carbons. More preferably, R is C1-C8 alkyl, and A and B are C4-C8 alkylene and Q is C4-C10 alkylene.
In a preferred embodiment, the polymer is prepared by polymerizing (a) polyamine having the formula:
H2N(CH2)x[NR(CH2)y]aNH2
or salts thereof, wherein x and y, which may be the same or different, are 4 to 10, a is 2 to 5, and R is an alkyl group containing 1 to 8 carbons in a straight or branched chain and (b) aliphatic and aromatic dicarboxylic acids or esters, such as adipic acid, dimethyl adipate, terephthalic acid, dimethyl terephthalate, isophthalic acid, dimethyl isophthalate, naphthalene dicarboxylic acid, dimethyl naphthalene dicarboxylate, or mixtures thereof. Preferred are adipic acid, dimethyl adipate, terephthalic acid, dimethyl terephthalate and mixtures thereof.
The polymers of this invention are useful in preparing acid-dyeable polymer compositions, and in this context, in the following sections of this document are referred to as xe2x80x9cpolymeric additive(s)xe2x80x9d or xe2x80x9cpolymer compound(s)xe2x80x9d and the other polymers, such as nylon or polyester are referred to as the xe2x80x9cpolymer(s).xe2x80x9d Such an acid-dyeable polymer comprises (a) polymer (e.g., nylon or polyester) and (b) the polymeric additive.
Preferred polymers are nylons and polyesters.
Nylon is acid-dyeable and the invention makes it possible to deep-dye nylon or tailor nylons to achieve desired colors. For instance, with this invention it is possible to prepare nylon compositions, fibers and other products which can be dyed to a deep shade. The invention is particularly useful with nylon 6, nylon 4,6, nylon 6,6, nylon 6,10, nylon 6,12, nylon 12,12 and copolymers thereof, and blends thereof.
The composition can be prepared by melt blending the polymer and the polymeric additive. The polymeric additive is added so that the amount of tertiary amine units is effective to promote acid-dyeability. Such compositions are useful in forming fibers, including monocomponent and multicomponent (e.g., bicomponent) fibers. For instance, it may be used as one or both component of a bicomponent fiber comprising poly(ethylene terephthalate) and poly(trimethylene terephthalate) components. The composition can also be used as a film or film layer.
The composition or products made therewith (e.g., fibers or films) can be acid dyed.